Shale gas is a particularly important research target on Chinese energy resources, especially in the Upper Yangtze region. Complex topography and geologic conditions challenge seismic exploration of shale gas in this area, and ground-based electromagnetic (EM) methods are used to aid recognition of the best reservoirs. However, the electrical properties of organic shale (EPOS) and its correlation to shale-gas petrology remain poorly understood. We studied EPOS and their correlation to shale petrology by measuring and analyzing the petrochemical features and complex impedance of rock samples from the Silurian Longmaxi and Cambrian Niutitang Formations in the Upper Yangtze, southwest China. Our study indicates that the organic shale in the Upper Yangtze features low resistivity and high polarizability in terms of a high negative phase, but no obvious low resistivity is observed among shaly sandstone and shales with lower and higher total organic carbon. Pyrite and quartz contents in the organic shale dominantly contribute to the EPOS with different mechanisms. Our result indicates that the EPOS bear relations to the petrology parameters of organic shale, which is essential for shale-gas evaluation and exploration. The correlation between EPOS and the shale-gas petrology promoted a new way for shale-gas exploration with complex geology, topography, and surface conditions in China, especially in the Upper Yangtze region, by using the ground-based EM method to evaluate the parameters of shale gas and to aid to delimit the productive reservoirs (“sweet spots”).